Manufacture of cellulose from lignocellulose materials



I Patented Dec. 3, 1935 UNITED STATES PATENT OFFICE MANUFACTURE OF CELLULOSE FROM LIGNOCELLULOSE MATERIALS No Drawing. Application March 14, 1935, Serial No. 11,068. In Great Britain April 4, 1934 12 Claims.

This invention relates to the manufacture of cellulose from lignocellulosic materials such as wood and the likeby processes in which lignin is removed from the materials in solution in organic 6 solvents or solvent mixtures.

In processes of this kind it has been proposed to employ in association with the organic solvent or solvent mixture about 0.1% or less of its weight of an acid or basic substance, in order to 10 assist in softening the lignocelluloslc materials, and so to increase their susceptibility. to attack by the organic extracting agent. The conditions of temperature and pressure needed to cause the organic solvent or solvent mixture to dissolve the lignin in a satisfactory manner are not perceptibly changed by this use of acid or basic substances.

According to the present invention lignln is removed from lignocellulosic materials in solution in organic solventsor solvent mixtures which contain sulphur dioxide, and/or inorganic basic -or alkaline substances in amount (reckoned as total inorganic substance) of at least 0.5% of the weight of the organic solvent or solvent mixture.

The use of such proportions of these inorganic substances in conjunction with the organic solvents -or solvent mixtures enables the extraction to be carried out at lower temperatures than have hitherto been practicable; gives a product containing a higher percentage of a-cellulose; and

' makes it possible to isolate considerable quantities of sugars from the used liquor.

Basic or alkaline substances are preferably employed in amount between about 2% and 8% or more, for example between 2 and 5%, of the solvent or solvent composition. Thus, for ex ample, an alcohol-water mixture containing 2 or 5% of sodium hydroxide may be employed.

When sulphur dioxide is used this may be present in similar proportions, although proportions down to about 0.5% or even lower proportions may also be employed with good results. As alreadyindicated, basic or alkaline substances and sul- 5 phur dioxide may be employed together, ior example, in the same amounts as if they were used separately; and the solvent or solvent mixture may contain excess of either the basic or alkaline substance or the sulphur dioxide, or these substances may be present in equivalent proportions,

' for example in the form of an alkali metal sulhite.

p The temperature at which the extraction is effected is preferably above C., for instance,

55 between and 175 C., and especially between about and 0., although higher temperatures may be employed if desired.

The extraction may be effected under the pressure generated by the extracting agents at the temperature employed or under a higher press- 5 sure; for example, pressures between 20 or 40 atmospheres and 100 atmospheres may be employed at a temperature of 120-155 C. or at other suitable temperatures. Such excess pressures may be obtained by means of a compressed 10 gas such as nitrogen having no substantial chemical effect on the extraction process.

Among the solvents and solvent mixtures that may be employed are alcohol-water, e. g. denatured alcohol-water, acetone-water, dioxane, l5 dioxane-water, alcohol-water-benzene, and many other mixtures, especially mixtures containing liquids of difierent polarities, as described, for example, in U. S. application S. No. 713,309 filed February 28, 1934, and particularly such mixtures 20 containing water, as described for example in U. S. application S. No. 2,862 filed January 22, 1935, and/or an alcohol or other hydroxy compound. The term organic solvent mixture" as used in the specification and claims includes 25 mixtures containing water and one or more organic components.

- To facilitate impregnation of the material by the solvent or solvent mixture, the former is preferably treated in a finely divided form. For ex- 30 ample, wood may advantageously be used in the form of chips or the like. The lignocellulosic material may be simply agitated with the solvent or solvent mixture, or to aid the impregnation the digester or other vessel containing the ma- 35 terial may be evacuated to any desired degree before introducing the solvent or solvent mixture. Other methods may be used to facilitate impregnation, for example, sudden release of pressure within the materials whereby the active sur- 40 face of the materials is increased to a very large extent. As described in U. S. application S. No. 565,203 filed September 25, 1931, such a process may be carried out by causing sudden vaporization of a liquid within the materials. Any other 45 method of securing an eflicient contact between the material and the solvent or solvent mixture may be employed.

The treatment of the ligno-cellulosic material with the solvent or solvent mixture may be effected in a single stage or twoor multi-stage process and in a continuous or discontinuous manner. For example the extraction may be performed in digesters or vessels such as are commonly employed in pulping processes, I

for example in. the sulphite process. In an other method of carrying out the invention the material may be subjected to a continuous extraction with the solvent or solvent mixture, for example as described in U. 8. application S. No. 727,608 filed May 26, 1934. The solvent or solvent mixture may, after the treatment, be cooled or distilled to re-precipitate the lignin and other substances contained therein and returned to the process.

If desired, the extraction of the lignin from the lignocellulosie materials may follow a preliminary treatment of the materials with hot or boiling water or water under pressure or with alkaline or acid solutions, but such preliminary treatment may, in general, be omitted. Moreover, the lignocellulosic material may if desired be subjected to other treatments prior to extraction by the process of the present invention, for example to treatments to remove resins. Such a treatment may consist in a simple extraction of the resin with benzene or a benzene-alcohol mixture. However, the resins are usually quite readily extracted in the process of the present invention, and a separate extraction is generally unnecessary unless the lignin is required in a more or less purified form.

.The cellulose produced by the process of the present invention may be employed, if desired after any other treatment, for any of the purposes for which cellulose is used, for example for the manufacture of cellulose esters or ethers, cellulose nitrate or cellulose xanthate, or for the manufacture of other cellulose derivatives, or for the manufacture of paper, especially the better classes of paper. In the case of the manufacture of cellulose acetate or other organic esters of cellulose it is advantageous to apply a pretreatment before carrying out the esterification process. Thus, the extracted cellulose may be subjected to treatment with lower fatty acids especially if a lower fatty acid has not already been employed in the extraction process. Again, a twostage pre-treatment may be applied such as that described in U. S. Patent No. 1,711,110 involving a preliminary treatment with hot dilute alkali or with cold strong alkali followed by a treatment with an organic acid and particularly a lower fatty acid.

The following examples illustrate the invention but do not in any way limit it:-

Example 1 Spruce chips are extracted at a temperature of 150 C. with a liquor containing equal parts by volume of ethyl alcohol and water and containing 2% of sulphur dioxide. The extraction is carried out in three stages, each lasting about 2 hours. Fresh solvent is employed for each stage and the total weight of solvent used in all three stages is about 6 times the weight of the chips.

The cellulose produced is washed with'a similar, but sulphur dioxide-free, alcohol-water mixture and is subjected to a chlorine bleach. The organic solvent liquor after use is freed from solids by distillation, and may then, after adjustment of the sulphur dioxide content, be used again; the solid residue comprises mainly lignin (partly in a sulphur-containing form) and water soluble sugars.

Example 2 Spruce chips are heated to a temperature of 145 C. for 12 hours in an autoclave with about 18 times their weight of a 2 solution of sodium hydroxide in a mixture of equal parts by volume of ethyl alcohol and water.

The cellulose produced is washed and treated as in Example 1, and the alcohol and water recovered from the liquor by distillation. 5

What we claim and desire to secure by Letters Patent is:--

1. Process forthe manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials by solution in organic solvents or solvent mixtures which con-- tain inorganic basic substances in amount between 0.5 and 8% of the organic solvent or solvent mixture.

2. Process for the manufacture of cellulose from 15 lignocellulosic materials, which comprises extracting lignin from the materials by solution in organic solvents or solvent mixtures which contain inorganic basic substances in amount between 2 and 8% of the organic solvent or solvent 20 mixture.

3. Process for the manufacture of cellulose from lignocellulosic materials, which comprises ex- V tracting lignin from the materials by solution in organic solvents or solvent mixtures which contain a caustic alkali in amount between 2 and 5% of the organic solvent or solvent mixture.

4. Process for the manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials at a temperature between 115 and 175 C.' by solution in organic solvents or solventmixtures which contain inorganic basic substances in amount between 0.5 and 8% of the organic solvent or solvent mixture. 5. Process for the manufacture of cellulose from 35 lignocellulosic materials, which comprises extracting lignin from the materials at a temperature between 115 and 175 C. by solution in organic solvents or solvent mixtures which contain a caustic alkali in amount between 2 and 5% of the organic solvent or solvent mixture.

6. Process for the manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials at a temperature between 120 and 155 C. by solution in organic solvents or solvent mixtures which contain a caustic alkali in amount between 2 and 5% of the organic solvent or solvent mixture.

7. Process for the manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials under a pressure between 20 and atmospheres by solution in organic solvents or solvent mixtures which contain inorganic basic substances in amount between 0.5 and 8% of the organic solvent or solvent mixture.

8. Process for the manufacture of cellulose from lignocellulosic materials, which comprises ex-v tracting lignin from the materials at a temperature between and 175 C. and under a pressure between 20 and 100 atmospheres by solution in organic solvents or solvent mixtures which contain a caustic alkali in amount between 2 and 5% of the organic solvent or solvent mixture.

9. Process for the manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials by solution in a mixture of ethyl alcohol and water containing a caustic alkali in amount between 2 and 5% of the organic solvent mixture.

10. Process for the manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials at a temperature between and C. by solution in a mixture of ethyl alcohol and water containing a 75 caustic alkali in amount between 2 and 5% of the organic solvent mixture.

11. Process for the manufacture of cellulose from lignocellulosic materials, which comprises extracting lignin from the materials by solution in a homogeneous mixture of ethyl alcohol, benzene and water containing a caustic alkali in amount between 2 and 5% or the organic solvent mixture.

12'. Process for the manufacture of cellulose from lign'ocellulosic materials, which comprises extracting lignin from the materials at a temperature between 120 and 155- C. by solution in a homogeneous mixture of ethyl alcohol, benzene and water containing a caustic alkali in amount between 2 and 5% of the organic solvent mixture.

WALTER HENRY GROOMBRIDGE. ERIC VERNON MEILERS. 

